T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy for ambient methane monitoring using 3.38-μm antimonide-distributed feedback laser diode

This paper reports on the development of a gas sensor involving a newly available 3.38-μm distributed feedback laser in combination with a novel T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy (T-mR QEPAS), capable of simultaneous monitoring of multi-species (such as CH₄, H₂CO, HCl, C₂H₄) using the same QEPAS spectrophone. As a first demonstration, monitoring of ambient methane (CH₄) was achieved at atmospheric pressure with a 1σ detection limit of 400 ppbv (parts per billion by volume) in an integration time of 10 s and a water vapor concentration of 1.15 vol% (11,500 ppm) in the atmosphere, which is very suitable for field measurement of CH₄ emission.     

Simultaneous CO concentration and temperature measurements using tunable diode laser absorption spectroscopy near 2.3 μm

Simultaneous measurements of carbon monoxide (CO) mole fraction and temperature using tunable diode laser absorption spectroscopy (TDLAS) near 2.3 μm are reported. The measurement method uses ro-vibrational transitions [R(27): v″ = 1 → v′ = 3] and [R(6): v″ = 0 → v′ = 2] in the first overtone band of CO near 2.3 μm (~4,278 cm^?1). The measurements were performed in the post flame environment of fuel rich premixed ethylene–air flames with a N₂ co-flow, stabilized over a water cooled McKenna burner. Non-uniformity in the temperature and CO mole fraction, along the absorption line of sight, in the mixing layer of the co-flow, was considered during data analysis. The TDLAS based temperature measurements (±80 K) were in good agreement with those obtained using N₂ vibrational coherent anti-Stokes Raman scattering (±20 K), and the CO mole fraction measurements were in good agreement with the equilibrium values, for equivalence ratios lower than 1.8. A signal to noise ratio of 45 was achieved at an equivalence ratio of 1 for a CO concentration of 0.8 % at 1,854 K.     

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

Gas sensing by tunable multimode diode laser using correlation spectroscopy

A novel method to use multimode diode lasers for gas detection is demonstrated. The relationship between the intensity decay of partially absorbed multiple modes and the target gas concentration is presented. The gas concentration is retrieved by a linear-regression-based procedure applied on simultaneously recorded absorption signals in a dual-beam wavelength-modulation configuration. Signals of non-gas origin or disturbed by interfering gases are effectively eliminated by correlation analysis procedure. Light intensity fluctuations and wavelength shifts due to temperature drift are automatically compensated for. Several absorption signals can readily be obtained within a limited tuning range by overlapping the laser multimode chart with the target gas spectrum. This scheme was applied on the detection of trace acetylene mixed in ambient air, and a sensitivity of 3 ppm was achieved with a 48.5 cm path length. The trade-off between sensitivity and reliability for retrieving gas concentration by multiple absorption signals is also presented.     

Laser diode photoacoustic and FTIR laser spectroscopy of formaldehyde in the 2.3 μm and 3.5 μm spectral range

The room temperature operating GaInAsSb/AlGaAsSb based diode laser and 66 K InAsSb/InAsSbP laser diode both operating in spectral range of formaldehyde absorption 4350-4361 cm⁻¹ and 2821-2823 cm⁻¹ have been characterized and compared. Very precise arrangement of laser absorption together with high resolution Fourier transform technique was tested. The photoacoustic technique was employed to determine the detection limit of formaldehyde (less than 1 ppmV) diluted by nitrogen for the strongest absorption line of the ν₃ + ν₅ band in the emission region of the GaInAsSb/AlGaAsSb diode laser. The detection limit (less than 10 ppbV) of formaldehyde was achieved in the 2820 cm⁻¹ spectral range in case of InAsSb/InAsSbP laser (fundamental bands of ν₁, ν₅)_.     

Detection of propane using tunable diode laser spectroscopy at 3.37 μm

We report Tunable Diode Laser Spectroscopy measurements of propane using a recently developed 3.37 μm GaInAsSb/AlGaInAsSb DFB laser. We have demonstrated that Wavelength Modulation Spectroscopy can be utilized to enhance a sharp feature in the broader propane spectrum around 3370.4 nm. A minimum detectable concentration of 30 ppb×m was obtained at a response time of 0.5 s. This corresponded to a minimum detectable absorption of 8 × 10^?5 which is why an improvement of the sensitivity by an order of magnitude is possible using this laser and a more optimized optical setup.     

Detection of HCl on the first and second overtone using semiconductor diode lasers at 1.7 μm and 1.2 μm

Sensitivity studies are also performed, to evaluate the minimum detectable concentration of HCl in air. Received: 7 August 1998/Revised version: 5 October 1998     

Laser diode spectroscopy of H2O at 2.63 μm for atmospheric applications

The 2.7 μm spectral range is highly suitable for the in situ monitoring of atmospheric H₂O using compact balloonborne laser diode spectrometers. Water vapour spectroscopic parameters of the 2₀₂   1₀₁ and the 4₁₃   4₁₄ transitions of the ν₃ band are revisited in this spectral region using a new distributed-feedback InGaAsSb laser diode emitting at 2.63 μm. Accurate line strengths are provided which are well adapted for the in situ probing of the middle atmosphere. Our measurements are thoroughly compared to an existing molecular database, laboratory measurements and ab-initio calculations. A laser hygrometer was developed for operation from small stratospheric balloons using this new laser diode technology, with emission at 2.6 μm. The realized sensor is described and results from a recent test-flight are reported. PACS 07.57.Ty; 92.60 Jq     

A near-infrared acetylene detection system based on a 1.534 μm tunable diode laser and a miniature gas chamber

A near-infrared (NIR) dual-channel differential acetylene (C₂H₂) detection system was experimentally demonstrated based on tunable diode laser absorption spectroscopy (TDLAS) technique and wavelength modulation spectroscopy (WMS) technique. A distributed feedback (DFB) laser modulated by a self-developed driver around 1.534 μm is used as light source. A miniature gas chamber with 15 cm path length is adopted as absorption pool, and an orthogonal lock-in amplifier is developed to extract the second harmonic (2f) signal. Sufficient standard C₂H₂ samples with different concentrations were prepared, and detailed measurements were carried out to study the detection performance. A good linear relationship is observed between the amplitude of the 2f signal and C₂H₂ concentration within the range of 200–10,000 ppm, and the relative measurement error is less than 5% within the whole range. A long-term monitoring lasting for 20 h on a 1000 ppm C₂H₂ sample was carried out, and the maximum concentration fluctuation is less than 2%. Due to the capability of using long-distance and low-loss optical fiber, the gas-cell can be placed in the filed for remote monitoring, which enables the system to have good prospects in industrial field.     

Simultaneous measurement of liquid water film thickness and vapor temperature using near-infrared tunable diode laser spectroscopy

A fiber-based multiplexed tunable diode-laser absorption sensor with three near-infrared distributed-feedback diode lasers at ∼1.4 μm is used for simultaneous nonintrusive measurements of liquid water film thickness and vapor-phase temperature. Water film thicknesses are derived from broad-band absorption determined at two fixed wavelengths while gas-phase temperature above the film is obtained via two-line thermometry using the fast wavelength tuning with line-integrating absorption. Probing the liquid film at two wavelengths with significantly different liquid-phase absorption cross sections allows discriminating against additional signal losses due to surface fowling, reflection, and beam steering. The technique is demonstrated for liquid layers of defined thicknesses and in time-resolved measurements of evaporating films.     

Ozone detection by differential absorption spectroscopy at ambient pressure with a 9.6 μm pulsed quantum-cascade laser

We report direct absorption spectroscopic detection of ozone at ambient pressure with a pulsed, DFB quantum-cascade laser (QCL) tuned within 1044–1050 cm^-1 by temperature scanning. Wavelength calibration curves were derived from FTIR and CO₂ spectra and interpreted with respect to the heat transfer from the heterostructure to the sink. The laser linewidth (0.13 cm^-1 FWHM) was found to decrease with temperature, probably as a result of operation at constant current. Spurious spectral features due to baseline inaccuracies were successfully filtered out from the QCL O₃ spectra using differential absorption. Reference O₃ concentrations were obtained by applying the same method to UV spectra, simultaneously measured with a differential optical absorption spectrometer (DOAS). Column densities retrieved from QCL spectra are in fairly good agreement (±20%) with the DOAS values above 28 ppmm. The estimated QCL lowest detectable, absolute and differential absorptions, (7×10^-3 and 2×10^-3, respectively), entail effective detection limits of 14 and 25 ppmm, respectively. Ongoing improvements in the acquisition system should allow the achievement of detection limits at the level of commercial open-path DOAS systems (2 ppmm) in the near future. Our results demonstrate the applicability of the differential absorption method to QCL spectroscopy at ambient pressure, and encourage its use for open path detection. PACS 42.62.Fi; 82.80.Gk; 92.60.Sz     

Temperature and current coefficients of lasing wavelength in tunable diode laser spectroscopy

The factors determining temperature and current coefficients of lasing wavelength are investigated and discussed under monitoring CO₂-gas absorption spectra. The diffusion rate of Joule heating at the active layer to the surrounding region is observed by monitoring the change in the junction voltage, which is a function of temperature and the wavelength (frequency) deviation under sinusoidal current modulation. Based on the experimental results, the time interval of monitoring the wavelength after changing the ambient temperature or injected current (scanning rate) has to be constant at least to eliminate the monitoring error induced by the deviation of lasing wavelength, though the temperature and current coefficients of lasing wavelength differ with the rate.     

Influence of laser intensity in second-harmonic detection with tunable diode laser multi-pass absorption spectroscopy

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detection. The ratio of the second-harmonic signal to the intensity of laser beam incident to the multi-pass cell is proved to be proportional to the product of the path length and the gas concentration under any condition. A new calibration method based on this relation in TDLAS system for the measurement of trace gas concentration is proposed for the first time. The detection limit and the sensitivity of the system are below 110 and 31ppbv （parts-per-billion in volume）, respectively.     

CH4/air/SO2 premixed flame spectroscopy with a 7.5-μm diode laser

As sulfur dioxide (SO₂) is often involved in combustion processes, we present here SO₂-concentration measurements in the post-flame region of a CH₄/air/SO₂ premixed flame. SO₂ concentrations were deduced from high-resolution absorption spectra recorded with a mid-infrared tunable diode-laser (TDL) source operating at liquid nitrogen temperature. Single-mode, continuous frequency tuning around 1384.5 cm^-1 (or 7.5 μm) is achieved by a fine TDL temperature ramp. These experiments lead us to develop in situ combustion-pollutant measurements with compact apparatus. We show that this non-intrusive method is efficient for detection and allows the retrieval of SO₂ concentration and temperature. Received: 19 February 2001 / Revised version: 18 April 2001 / Published online: 7 June 2001     

Fiber-distributed multi-channel open-path H_2S sensor based on tunable diode laser absorption spectroscopy

Tunable diode laser based gas detectors are now being used in a wide variety of applications for safety and environmental interest. A fiber-distributed multi-channel open-path H2S sensor based on tunable diode laser absorption spectroscopy (TDLAS) is developed, the laser used is a telecommunication near infrared distributed feed-back (DFB) tunable diode laser, combining with wavelength modulation spectroscopy technology, a detection limit of 20 ppm·m is demonstrated. Multi-channel detection is achieved by combining optical fiber technique. An on-board reference cell provides on-line sensor calibration and almost maintenance-free operation. The sensor is suitable for large area field H2S monitoring application.     

Antimonide-based lasers and DFB laser diodes in the 2–2.7 μm wavelength range for absorption spectroscopy

We report on Fabry–Pérot semiconductor lasers and single frequency distributed feedback lasers based on GaInAsSb/AlGaAsSb quantum wells. The laser structures were grown by molecular beam epitaxy on GaSb substrates. The devices were etched either by wet process or by inductively coupled plasma (ICP) process. Electron-beam lithography was used to deposit a metal Bragg grating on each side of the laser ridge to fabricate the DFB lasers. The devices all operate in the continuous wave regime at room temperature with a single frequency emission above 2.6 μm and good tuning properties, making them well adapted to tunable diode laser absorption spectroscopy. PACS 42.55.Px; 42.62.Fi